JP2008007629A - Aqueous coloring material and powdery coloring material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a powdery coloring material comprising polyion complex fine particles in combination with a polymer dye, in which an average particle diameter is small and particle size distribution is also small, and storage stability is excellent, and also provide a powdery coloring material obtained by drying the same. <P>SOLUTION: An aqueous coloring material comprises (I) a polymer compound containing (A) an epoxy resin residue, (B) a cationic hydrophilic polymer segment and (C) a nonionic hydrophilic polymer segment, and (II) a coloring compound containing an anionic group. One embodiment of the material is one wherein the epoxy resin residue (A) is obtained by drying colloidal aqueous coloring agent hydrophobically combined in an aqueous medium. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an aqueous coloring material and a powdered coloring material, and more specifically, an aqueous coloring that can be suitably used for various inks such as an aqueous ink such as an ink jet ink, a display member such as a color filter, and an automobile paint. The present invention relates to a material and a powdered coloring material obtained by drying it.

  In recent years, polymers that have oppositely charged charges and dyes have been used as a technique to achieve the water resistance and light resistance of pigments without compromising the variety of colors, the vividness of the colors, and the high saturation. In combination, these are attracted by electrostatic force, and at the same time, stacking is caused by the interaction between the π-electron planes of dye molecules which are widely spread, and a technique of polyion complex (PIC) has been known. The PIC thus obtained has crystallinity, is a means capable of preventing bleeding, which is a weak point of the dye, and improving light resistance, water resistance, gas resistance, and the like. For example, when both aqueous solutions of a cationic polymer and an anionic dye are mixed, the cationic portion and the anionic portion cancel each other and become hydrophobic, so that a water-insoluble PIC solid can be obtained ( For example, refer nonpatent literature 1.).

  However, since the water-insoluble PIC solid proposed in Non-Patent Document 1 easily precipitates in water, when this is used as an aqueous coloring material, a dispersion synthesized separately as in the case of pigment dispersion. It is necessary to add a resin and adsorb the resin while pulverizing it with a strong shearing force, which requires a large capital investment and unnecessary power, and a solution is required.

  As means for solving the above problems, for example, from a block copolymer or graft copolymer having an ionic hydrophilic polymer unit and a nonionic hydrophilic polymer unit, and a coloring compound having an ionic group An aqueous coloring material has been proposed (see, for example, Patent Document 1).

  Although a dispersion having a small average particle diameter is obtained by the method proposed in Patent Document 1 and an aqueous coloring material can be obtained without using the above-described apparatus, coarse particles considered to be due to fusion between PICs. Because it occurs, its particle size distribution range is wide, and there are few parts with the appropriate particle size when used as a coloring material, so the yield is poor, and the factors that cause blisters when coating and coating This may cause clogging of the head portion of the apparatus, and furthermore, the fusion occurs during storage, so that the storage stability is poor, and there is still a problem for practical use.

C. F. J. et al. Faul, M.M. Antonietti, Chem. Eur. J. et al. , 2002, 12, 1276-2768. JP 2005-036039 A

  In view of the above situation, the problem to be solved by the present invention is an aqueous coloring material composed of fine particles of PIC combining a polymer and a dye, the average particle size of which is small and the particle size distribution is narrow, and the storage stability is excellent. Another object of the present invention is to provide a powdered coloring material obtained by drying it.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies and found that, in an aqueous medium, a specific hydrophobic core portion, a cationic hydrophilic polymer segment, and a nonionic hydrophilic polymer segment. It has been found that by combining a polymer compound capable of forming fine particles having a shell portion having a colorant and a coloring compound having an anionic group, fine particles comprising a polyion complex having a narrow particle size distribution range can be obtained. The present invention has been completed.

  That is, the present invention provides a polymer compound (I) having an epoxy resin residue (A), a cationic hydrophilic polymer segment (B), and a nonionic hydrophilic polymer segment (C), and an anionic group. It is intended to provide an aqueous coloring material containing the coloring compound (II) having, and a powdery coloring material obtained by drying the aqueous coloring material.

  According to the present invention, it is possible to provide an aqueous coloring material composed of PIC which is excellent in water resistance, light resistance, coloring property, dispersion stability and storage stability and has a narrow particle size distribution width. The water-based coloring material solves the respective problems of dyes and pigments, is easy to handle, and can be suitably used for ink-jet inks, water-based paints, printing water-based inks, paints, and the like. . Moreover, it can use suitably also for a photo-alignment film | membrane, a color filter etc. as a raw material relevant to an optical device. Furthermore, the aqueous coloring material of the present invention is stabilized in a colloidal form in which the hydrophobic portions of the polymer compound are associated with each other in the aqueous medium to form the core portion, and the hydrophilic portion is the shell portion. By drying this, a powdery coloring material can be easily obtained. This coloring material is excellent in redispersibility in an aqueous medium, and can be suitably used for application to an aqueous paint or the like.

  The aqueous coloring material of the present invention comprises a polymer compound (I) having an epoxy resin residue (A), a cationic hydrophilic polymer segment (B), and a nonionic hydrophilic polymer segment (C), an anionic property And a coloring compound (II) having a group.

[Epoxy resin residue (A)]
The epoxy resin residue (A) in the polymer compound (I) used in the present invention has hydrophobicity, and is hydrophobically bonded to each other between molecules and / or molecules of the polymer compound (I) in an aqueous medium. It is a structure necessary for forming a hydrophobic core part, and has skeletons derived from various epoxy resins. The residue (A) is bonded to the cationic hydrophilic polymer segment (B) and / or nonionic hydrophilic polymer segment (C) described later via an epoxy group or a hydroxyl group of an epoxy resin used as a raw material. is doing. The epoxy resin that can be used as a raw material is not particularly limited, but a bisphenol type epoxy resin can be obtained because a more stable aqueous coloring material (aqueous dispersion) can be obtained and industrial availability is easy. It is preferable to use a naphthalene type tetrafunctional epoxy resin and a tetraphenylolethane type epoxy resin, and it is particularly preferable to use a bisphenol A type epoxy resin and a naphthalene type tetrafunctional epoxy resin. The number average molecular weight of the epoxy resin residue (A) in the polymer compound (I) is preferably in the range of 300 to 10,000, and more preferably in the range of 500 to 3,000. In addition, it is preferable in that an aqueous coloring material having a small particle diameter can be obtained.

  The above-mentioned epoxy resin has a plurality of epoxy groups per molecule, but is previously partially bonded to the cationic hydrophilic polymer segment (B) and the nonionic hydrophilic polymer segment (C). In particular, the oxirane ring in the epoxy group may be opened and used.

  Examples of the substance for opening such an oxirane ring include various alcohols, phenols, secondary amines, etc., and examples thereof include aliphatic alcohols having 1 to 20 carbon atoms, and substituents on aromatic rings. Phenols that may be substituted, phenylphenols that may have a substituent on the aromatic ring, various dialkylamines such as dimethylamine, diethylamine, dibutylamine, dihexylamine, etc. According to the introduction method and introduction ratio of the cationic hydrophilic polymer segment (B) and the nonionic hydrophilic polymer segment (C) to the polymer compound (I), the type and amount of use should be adjusted appropriately. Is preferred.

[Cationic hydrophilic polymer segment (B)]
The cationic hydrophilic polymer segment (B) in the polymer compound (I) used in the present invention is a polymer chain having a cationic group, and a coloring compound (II) having an anionic group described later and This segment is necessary for ionic bonding, whereby the coloring compound (II) can be immobilized in the polymer compound (I) or the aggregate of the polymer compound (I). Examples of the cationic group include those obtained by protonating or quaternizing a nitrogen atom contained in a primary amine, secondary amine, tertiary amine, pyridine ring or the like.

  Examples of the cationic hydrophilic polymer segment (B) include those obtained by cationizing a segment composed of a polymer composed of polyethyleneimine, polyvinylamine, polyallylamine, polyvinylpyridine, etc. Among these, more Since a stable aqueous coloring material (aqueous dispersion) can be obtained, it is preferable that the segment made of polyethyleneimine is cationized. Examples of the cationization method include protonation with hydrochloric acid and the like and quaternary chlorination with iodomethane and the like.

  The molecular weight of the segment (B) is preferably in the range of 100 to 10,000 from the viewpoint of obtaining particles having a small particle size and high crystallinity, and particularly 1, It is preferably in the range of 000 to 8,000.

  Further, all the monomer units forming the cationic hydrophilic polymer segment (B) may not be cationized, and within 50 mol% or less, preferably 30 mol% or less of all units, Sex units may be included randomly.

  For example, as a hydrophilic monomer used as a raw material for the polymer forming the segment, a nonionic unit is obtained by a method in which a cationizable monomer and a nonionic monomer are used in combination, and these are copolymerized and then cationized. Can be introduced.

  Examples of the nonionic unit include N-acetylethyleneimine, N-formylethyleneimine, N-propionylethyleneimine, N-acetylvinylamine, N-formylvinylamine, N-acetylallylamine, N-formylallylamine and the like. Amides, allylamines, vinylamines, reaction products of ethyleneimines with acid halides such as benzoyl chloride, reaction products of lactones such as β-butyrolactone, lactide, phenyl isocyanate, hexyl isocyanate, etc. The unit which consists of a reaction product etc. with isocyanate of this can be mentioned.

  When the cationic hydrophilic polymer segment (B) is a segment made of polyethyleneimine, for example, after living polymerization of oxazolines to obtain polyoxazoline, 50 mol% or more thereof is hydrochloric acid or water. By hydrolysis using an aqueous sodium oxide solution or the like, a segment containing a cationized (hydrochlorinated) ethyleneimine unit and a nonionic oxazoline unit can be obtained.

[Nonionic hydrophilic polymer segment (C)]
The nonionic hydrophilic polymer segment (C) in the polymer compound (I) used in the present invention is a polymer compound (I) or an aggregate of the polymer compound (I) in an aqueous medium, or an anionic property described later. This segment is necessary for stably presenting fine particles composed of PIC ion-bonded with the coloring compound (II) having a group. Examples of the segment (C) include monomers such as ethylene glycol, vinyl acetate, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, N-vinylcaprolactam, (meth) acrylamide, and (meth) acrylic acid esters. A segment made of a polymer (polyethylene glycol) obtained by polymerizing ethylene glycol in view of excellent storage stability of the resulting aqueous coloring material (aqueous dispersion). It is preferable.

  The molecular weight of the segment (C) is preferably in the range of 100 to 10,000 from the viewpoint of obtaining particles having a small particle size and high crystallinity, and particularly 1, A range of 000 to 8,000 is more preferable.

[Shape of polymer compound (I)]
The shape of the polymer compound (I) used in the present invention is not particularly limited, and any shape such as a linear shape, a star shape, or a hyperbranched shape can be used. You may mix and use. Furthermore, two or more types of polymer compounds (I) having different shapes can be used in combination. For example, polymers having different shapes such as a linear epoxy resin residue (A), a star-shaped cationic hydrophilic polymer segment (B), and a non-ionic hydrophilic polymer segment (C) are linear. Combined ones can also be used.

  Among these, when the epoxy resin residue (A) that is hydrophobic and the cationic hydrophilic polymer segment (B) are directly chemically bonded, the cationic hydrophilic polymer segment (B) and the postscript are described below. Ionic bond with the coloring compound (II) having an anionic group to form a hydrophobic PIC moiety in the vicinity of the epoxy resin residue (A), and in the aqueous medium, nonionic hydrophilic so as to surround it The conductive polymer segment (C) is present, and fine particles composed of PIC having a more stable, small average particle size and narrow particle size distribution are obtained, which is a preferable shape.

That is, as a preferable form of the polymer compound (I), the following general formula (1)
A-[(BC) _n ] _m (1)
[In Formula (1), A is an epoxy resin residue, B is a cationic hydrophilic polymer segment, C is a nonionic hydrophilic polymer segment, n is 1 or more, and m is 1 -10. Where n is the number of repeats of a multi-block segment (BC) in which two segments B and C are bonded, and m is the number of chains in which the multi-block segment repeats are chemically bonded to one A It is. ]
Or the following general formula (2)
A- [B- (C) _p ] _q (2)
[In Formula (2), A, B, and C are the same as the above, p is larger than 1, and q is 1-10. Here, p represents the number of C bonded to B, and q is the number of B- (C) _p chemically bonded to one A. ]
Etc.

  The polymer compound (I) used in the present invention contains an epoxy resin residue (A), a cationic hydrophilic polymer segment (B), and a nonionic hydrophilic polymer segment (C) as described above. However, the number average molecular weight of the polymer compound is preferably in the range of 500 to 50,000 from the viewpoint that the obtained water-based coloring material has a small average particle diameter and a narrow distribution width is obtained. In particular, it is preferably 3,000 to 40,000. Also, the weight average molecular weight is preferably in the range of 500 to 100,000 for the same reason, and particularly preferably in the range of 3,000 to 80,000.

  The mass of the epoxy resin residue (A) in the polymer compound (I) is Wa, the mass of the cationic hydrophilic polymer segment (B) is Wb, and the mass of the nonionic hydrophilic polymer segment (C). When Wc is Wa / (Wa + Wb + Wc) = 0.03 to 0.8 and Wb / (Wb + Wc) = 0.1 to 0.9 (mass ratio), good particle size distribution And a powdery coloring material obtained by drying it can be obtained. In particular, Wa / (Wa + Wb + Wc) = 0.05 to 0.3 and Wb / (Wb + Wc) = 0.5 to 0 .8 (mass ratio) is preferable because the average particle size is small and the storage stability is excellent.

[Method for Producing Polymer Compound (I)]
The polymer compound (I) used in the present invention is not particularly limited as long as it has the above-described constituent components. As a method for easily synthesizing a polymer compound as designed, for example, (i) an epoxy resin is reacted with a hydroxyl group-containing compound to open an oxirane ring, and the hydroxyl group produced at this time is tosylated to polymerize. Grants starting ability. Using the obtained compound as a polymerization initiator, a monomer such as oxazoline that becomes a precursor of a cationic hydrophilic polymer segment is polymerized, and a nonionic hydrophilic polymer such as polyethylene glycol is further reacted at the terminal to increase the polymer. This is a molecular compound. Thereafter, hydrolysis of the polyoxazoline moiety using hydrochloric acid, aqueous sodium hydroxide, or the like, and protonation of the nitrogen atom in the resulting polyalkyleneimine chain, to obtain the desired polymer compound. (Ii) A method in which an epoxy resin is reacted with an amine or polymer thereof modified in advance with a nonionic hydrophilic polymer such as polyethylene glycol, and the amino group portion of the resulting polymer compound is cationized. It is done. In particular, when the latter method is employed and a polyfunctional amine is used, a part of the oxirane ring in the epoxy resin used in advance is opened with various reactive compounds such as a hydroxy compound, thereby functionalizing the oxirane ring. It is preferable to reduce the base concentration and take measures to prevent the formation of a gel-like product insoluble in water.

[Dispersion of polymer compound (I)]
The polymer compound (I) used in the present invention forms an O / W type dispersion in a substantially aqueous medium. Since this particle size is often reflected in the particle size of the dispersion of the aqueous coloring material, reducing the particle size of the polymer compound (I) reduces the particle size of the aqueous coloring material, and thus powder coloring. It is important from the point of manufacturing the material. Therefore, when preparing the dispersion of the polymer compound (I), it is preferable to perform an operation for reducing the particle size such as ultrasonic dispersion treatment or high-pressure dispersion treatment.

[Coloring Compound (II) Having Anionic Functional Group]
The coloring compound (II) having an anionic functional group used in the present invention is not particularly limited and is a general compound having a salt structure of an acidic functional group such as a sulfonate structure or a carboxylate structure. Any compound can be used. Classifying this mainly includes acid dyes, acid mordant dyes, direct dyes, reactive dyes and the like. Among these, a compound containing a sulfonic acid alkali metal salt or a carboxylic acid alkali metal salt portion is preferable as the coloring compound (II) used in the present invention.

  The coloring compound (II) having an anionic functional group is generally called a dye, and is exemplified by a color index number. I. Acid Black 1, 2, 3, 7, 24, 26, 29, 31, 48, 50, 51, 52, 58, 60, 62, 63, 64, 67, 72, 76, 77, 94, 107, 108, 109, 110, 112, 115, 118, 119, 121, 122, 132, 139, 140, 155, 156, 157, 158, 159, 182, 191, 194, C.I. I. Food Black 2, C.I. I. Direct Black 17, 19, 22, 32, 35, 38, 51, 56, 62, 71, 74, 75, 77, 94, 105, 106, 107, 108, 112, 113, 117, 118, 132, 133, 146, 154, 168, 171, 195, 200, C.I. I. Reactive black 1, 3, 4, 5, 6, 8, 9, 10, 12, 13, 14, 18, 31, and hydrolysates thereof can be used.

  Examples of blue dyes include C.I. I. Acid Blue 1, 7, 9, 15, 22, 23, 25, 27, 29, 40, 41, 43, 45, 54, 59, 60, 62, 72, 74, 78, 80, 82, 83, 90, 92, 93, 100, 102, 103, 104, 112, 113, 117, 120, 126, 127, 129, 130, 131, 138, 140, 142, 143, 151, 154, 158, 161, 166, 167, 168, 170, 171, 182, 183, 184, 187, 192, 199, 202, 203, 204, 205, 229, 234, 236, 249, C.I. I. Direct Blue 1, 2, 6, 15, 22, 25, 41, 71, 76, 77, 78, 80, 86, 87, 90, 98, 106, 108, 120, 123, 158, 160, 163, 165, 168, 192, 193, 194, 195, 196, 199, 200, 201, 202, 203, 207, 225, 226, 236, 237, 246, 248, 249, C.I. I. Reactive Blue 1, 2, 3, 4, 5, 7, 8, 9, 13, 14, 15, 17, 18, 19, 20, 21, 25, 26, 27, 28, 29, 31, 32, 33 , 34, 37, 38, 39, 40, 41, 43, 44, 46, and hydrolysates thereof.

  Examples of the red dye include C.I. I. Acid Red 1, 6, 8, 9, 13, 14, 18, 26, 27, 32, 33, 35, 37, 42, 49, 50, 51, 52, 57, 75, 77, 80, 82, 83, 85, 87, 88, 89, 92, 93, 94, 95, 97, 98, 106, 111, 114, 115, 117, 118, 119, 129, 130, 131, 133, 134, 138, 143, 145, 154, 155, 158, 168, 180, 183, 184, 186, 194, 198, 209, 211, 215, 252, 252, 254, 262, 265, 274, 282, 287, 289, 303, 306, 317, 320, 321, 322, 337, 356, C.I. I. Direct Red 1, 2, 4, 9, 11, 13, 17, 20, 23, 24, 28, 31, 33, 37, 39, 44, 46, 62, 63, 75, 79, 80, 81, 83, 84, 89, 95, 99, 113, 197, 201, 218, 220, 224, 225, 226, 227, 228, 229, 230, 231, C.I. I. Reactive Red 1, 2, 3, 4, 5, 6, 7, 8, 11, 12, 13, 15, 16, 17, 19, 20, 21, 22, 23, 24, 28, 29, 31, 32 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 46, 49, 50, 58, 59, 63, 64, 180 and their hydrolysates, food red 1 , 6, 11, 13, 17 and the like.

  Examples of yellow dyes include C.I. I. Acid Yellow 1, 2, 3, 7, 11, 17, 19, 23, 25, 29, 36, 38, 40, 42, 44, 49, 59, 61, 65, 70, 72, 73, 75, 76, 78, 98, 99, 104, 110, 111, 127, 131, 135, 142, 155, 162, 165, 183, 184, 194, C.I. I. Direct yellow 1, 8, 11, 12, 24, 26, 27, 33, 39, 44, 50, 85, 86, 87, 88, 89, 98, 106, 110, 132, 142, 144, 173, 194, C. I. Reactive yellow 1, 2, 3, 4, 6, 7, 11, 12, 13, 14, 15, 16, 17, 18, 22, 23, 24, 25, 26, 27, 37, 42 and their water Decomposition product, C.I. I. Food yellow 3, 4, 6, 7, 8, 9, etc. can be mentioned.

  In addition, C.I. I. Acid Violet 9, 15, 31, 34, 41, 43, 48, 49, 51, 66, 126, C.I. I. Direct violet 107, C.I. I. Acid Orange 7, 10, 20, 24, C.I. I. Direct Orange 22, C.I. I. Acid Brown 13, 27, 103, 126, 237, 289, 362, C.I. I. Acid green 1, 3, 5, 9, 16, 25, 27, 36, 40, 41, 44, 81 can also be used.

  In addition, pigment molecules with functional groups that can easily generate negative ions such as sulfonic acid, such as tetrasodium salt of copper phthalocyanine tetrasulfonate and quinacridone sulfonate, and raw materials for some lake pigments Such as those having low hydrophilicity and transition metal complexes using various organic dyes can be preferably used.

[Aqueous coloring material]
As the use ratio of the polymer compound (I) and the colorable compound (II), the colorant compound relative to the number of moles of cations in the cationic hydrophilic polymer segment (B) in the polymer compound (I) ( II) The value represented by the ratio of the number of moles of anions (anion / cation) is usually 0.05 / 1 to 0.95 / 1, and 0.05 / It is preferably 1 to 0.5 / 1, and particularly preferably 0.05 / 1 to 0.3 / 1. In addition, when it is difficult to calculate the molecular weight because the coloring compound (II) forms a complex, the use ratio of the polymer compound (I) and the coloring compound (II) is adjusted by the mass ratio. In this case, the colorant compound (II) / polymer compound (I) is preferably in the range of 0.05 / 1 to 6/1 (mass ratio). A range of 5/1 to 4/1 is preferable.

  In addition, the sum of the number of cationized basic groups and non-cationized basic groups in the polymer compound (I) is x (equivalent), and the number of coloring compounds (II) having an anionic group is determined. When y (equivalent) is set, the value of x / y is preferably in the range of 0.2 to 5, and more preferably in the range of 0.5 to 1.5. When the value is larger than this, the number of the coloring compound (II) having an anionic group contained in the polymer compound (I) becomes very small, resulting in faint coloring or the obtained aqueous coloring. Since the crystallinity of the material is lowered, color fastness and light resistance when used as a coloring material may be lowered. On the other hand, when the value is smaller than this, the amount of the coloring compound (II) having an anionic group becomes too large, and it is not sufficiently fixed in the PIC, and the color fastness and light resistance when used as a coloring material. May be low.

As a quantification method regarding the ratio of the polymer compound (I) and the colorable compound (II) in the obtained aqueous coloring material, for example, a method for determining the abundance ratio of functional groups by elemental analysis, A method of comparing the amount used and the amount of non-volatile content after being dried at 150 ° C., separately obtaining the concentration of the coloring compound (II) by a visible light absorption spectrum, etc., and calculating from these values, alkali The dispersion can be decomposed by a method such as a method of measuring by ¹ H-NMR and calculating the ratio from each typical peak intensity.

[Method for producing aqueous coloring material]
The method for producing the aqueous coloring material of the present invention is not particularly limited, and an operation in which the aqueous solution of the polymer compound (I) and the aqueous solution of the coloring compound (II) having an anionic group are combined and stirred. Alternatively, it can be produced by performing two operations of vibrating sequentially, alternately or simultaneously, but it is preferable to combine them while performing a stirring operation. By mixing together while stirring, the hydrophobic polyion complex formed by the cationic part in the polymer compound (I) and the anionic part in the coloring compound (II) does not become a large mass, and a fine dispersion It becomes easy to make.

  As the operation for combining the two kinds of aqueous solutions, the aqueous solution of the polymer compound (I) is added to the aqueous solution of the color compound (II), and the aqueous solution of the color compound (II) is the aqueous solution of the polymer compound (I). Or both of them may be added to the third container, and other organic solvents and polymers other than water can be added within a range not impairing the effects of the present invention. .

  Examples of the purpose of adding the other organic solvents and polymers include viscosity adjustment, adjustment of rheological properties, permeability to paper and various surfaces, adjustment of solubility, and the like, and inhibition of the formation of coarse particles. Thus, the particle size distribution width may be narrowed or the dispersion stability may be improved.

  Examples of organic solvents that can be used include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, isopropyl acetate and methyl acetate, carbonates such as ethylene carbonate and propylene carbonate, methanol, ethanol, ethylene glycol, Alcohols such as glycerin and polyvinyl alcohol, tetrahydrofuran (THF), dioxane, diethylene glycol, triethylene glycol, triethylene glycol monobutyl ether, polyethylene glycol, polyethylene glycol-polypropylene glycol copolymer and other cyclic or acyclic ethers, dimethylformamide Cyclic or acyclic amides such as dimethylacetamide and N-methylpyrrolidone, dimethylsulfoxide Sulfoxides, pyridine, dimethyl imidazolidinone, methylene chloride, and the like of.

  It is preferable that stirring of the dispersion obtained by the above operation is continued for a while after mixing. By carrying out such “ripening operation”, the particle size of the resulting dispersion (fine particles) is reduced, the dispersion stability is improved, and it is prevented from fusing and becoming larger when stored for a long time. An effect is obtained.

  In order to further reduce the particle size of the obtained dispersion, it is also preferable to perform ultrasonic dispersion treatment, high-pressure homogenizer treatment, or the like.

  In the mixture obtained above, the coloring compound (II) that has not been incorporated into the dispersion can be removed by a technique such as dialysis or ultrafiltration.

  The aqueous coloring material of the present invention has a core portion formed by hydrophobic association of epoxy resin residue portions in an aqueous medium, and a colored hydrophobic association portion exists around the core portion. Colloidal particle-like aqueous solution that has good water dispersibility without using other dispersants and the hydrophobic association part shows good colorability by covering the periphery with a hydrophilic part It is a coloring material. In the hydrophobic association part, the coloring compound (II) having a large number of anionic groups is formed by ionic bonding between the coloring compound (II) having an anionic group and the cationic hydrophilic polymer segment (B). Are concentrated along the chain of the polymer compound (I). In the concentrated state, strong π-π stacking occurs between the coloring compound (II) molecules having an anionic group, and the coloring compound (II) is not molecularly dispersed but has a certain regular association structure. Easy to form. Therefore, the obtained coloring material has excellent water resistance and light resistance.

  As the particle size of the colloidal aqueous coloring material, the degree of polymerization of the polymer compound (I) used and the composition of the cationic hydrophilic polymer segment (B) in the polymer compound (I) are adjusted. The particle size tends to increase as the degree of polymerization increases or as the content of the cationic hydrophilic polymer segment (B) increases. The degree of polymerization and the composition of the segment (B) need to be appropriately adjusted depending on the type and structure of the other components (epoxy resin residue and nonionic hydrophilic polymer segment) of the polymer compound (I) to be used. However, in order to obtain a stable colloidal particulate water-based coloring material, it is preferable to control the average particle size within a range of about 20 nm to 5 μm, and particularly within the range of 100 nm to 1 μm from the viewpoint of excellent storage stability. Preferably, the aqueous coloring material of the present invention is easily controlled within this range.

  Such a colloidal particulate aqueous coloring material can be made into a powdery coloring material that is easy to handle by removing the aqueous medium as a dispersion medium and drying it. The method for removing the aqueous medium is not particularly limited. For example, the aqueous medium can be easily evaporated by heating to 50 to 120 ° C. When the powdered coloring material obtained is returned again to the aqueous medium, it can be easily dispersed without any other dispersant.

  Thus, the aqueous coloring material of the present invention not only has the same coloring power when compared with a coloring compound (dye) in which the molecule is in an isolated state by taking the form of a polyion complex dispersion, Remarkably long endurance time and fastness to coloring against water and organic solvents can be provided. In addition, the particle size can be easily controlled, and it has good dispersibility without using a dispersant, and is excellent in water resistance and light resistance. Therefore, the water-based coloring material of the present invention can be suitably used for ink-jet inks, water-based paints, printing water-based inks, paints and the like. Moreover, it can use suitably also for a photo-alignment film | membrane, a color filter etc. as a raw material relevant to an optical device.

  Hereinafter, the present invention will be described in more detail with reference to examples. Unless otherwise specified, “%” represents “mass%”.

Synthesis Example 1 [Synthesis of block polymer comprising polyethylene glycol and polyethyleneimine]
Under a nitrogen atmosphere, 9.6 g of p-toluenesulfonic acid chloride was added to a mixed solution of 20.0 g (10.0 mmol) of methoxypolyethylene glycol [Mn = 2,000], 8.0 g (100.0 mmol) of pyridine and 20 ml of chloroform ( A chloroform (30 ml) solution containing 50.0 mmol) was added dropwise over 30 minutes while stirring with ice cooling. After completion of dropping, the mixture was further stirred at a bath temperature of 40 ° C. for 4 hours. After completion of the reaction, 50 ml of chloroform was added to dilute the reaction solution. Subsequently, after sequentially washing with 100 ml of 5% hydrochloric acid aqueous solution, 100 ml of saturated aqueous sodium hydrogen carbonate solution and 100 ml of saturated saline solution, it was dried over magnesium sulfate, filtered and concentrated under reduced pressure. The obtained solid was washed several times with hexane, filtered, and dried under reduced pressure at 80 ° C. to obtain 22.0 g of a tosylated product.

¹ H-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) measurement results are shown below.
¹ H-NMR (CDCl ₃ ) measurement result:
δ (ppm): 7.82 (d), 7.28 (d), 3.74-3.54 (bs), 3.41 (s), 2.40 (s)

  5.39 g (2.5 mmol) of a methoxypolyethylene glycol compound having a p-toluenesulfonyloxy group at the terminal synthesized above, polyethyleneimine (Epomin SP-200, manufactured by Nippon Shokubai Co., Ltd.) 8.0 g (0.8 mmol), 0.07 g of potassium carbonate and 50 ml of N, N-dimethylacetamide were placed in a flask and stirred at 100 ° C. for 6 hours under a nitrogen atmosphere. To the resulting reaction mixture, 200 ml of a mixed solution of ethyl acetate and hexane (V / V = 1/2) was added, and the mixture was vigorously stirred at room temperature (25 ° C.), and then the product solid was filtered. The solid was washed twice with 100 ml of a mixed solution of ethyl acetate and hexane (V / V = 1/2) and then dried under reduced pressure to obtain 12.7 g of a polymer solid consisting of polyethylene glycol and polyethyleneimine. It was.

¹ H-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) measurement results are shown below.
¹ H-NMR (CDCl ₃ ) measurement result:
δ (ppm): 3.50 (s), 3.05 to 2.20 (m)

Synthesis Example 2 [Synthesis of Polymer Compound (I-1) Consisting of Bisphenol A Type Epoxy Resin, Polyethylene Glycol, and Polyethyleneimine]
EPICLON AM-040-P (trade name, epoxy equivalent 933, manufactured by Dainippon Ink & Chemicals, Inc.) as a bisphenol A type epoxy resin, 18.7 g (20 m equivalent), 4-phenylphenol 1.28 g (7.5 mmol), A 65% ethyl acetate triphenylphosphonium ethanol solution (0.26 ml, 0.12 mol%) and N, N-dimethylacetamide (50 ml) were mixed and reacted at 120 ° C. for 6 hours in a nitrogen atmosphere. After standing to cool, it was dropped into 150 ml of water, and the resulting precipitate was washed twice with methanol and then dried under reduced pressure at 60 ° C. to obtain a monofunctional epoxy resin. The yield of the obtained product was 19.9g.

¹ H-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) is measured, and as a result of consideration of the integration ratio of epoxy groups, 0.95 oxirane rings remain in one molecule, and it is a monofunctional epoxy resin It was confirmed.

  To 1.0 g of the obtained monofunctional epoxy resin, 4.0 g of the polymer composed of polyethylene glycol and polyethyleneimine obtained in Synthesis Example 1, 15 ml of acetone and 40 ml of methanol are added, and the mixture is kept at 50 ° C. for 2 hours under a nitrogen atmosphere. The reaction was carried out with stirring. After completion of the reaction, acetone and methanol were removed under reduced pressure at 40 ° C. to obtain an aqueous solution of the polymer compound (I-1).

  The number average molecular weight of the epoxy resin residue (A) of the obtained polymer compound (I-1) is 1930, the average degree of polymerization of the cationic hydrophilic polymer segment is about 233, and the average degree of polymerization of the nonionic hydrophilic segment. Is about 45, the weight of the epoxy resin residue in the polymer compound (I) is Wa, the weight of the cationic hydrophilic polymer segment is Wb, and the weight of the nonionic hydrophilic polymer segment is Wc. /(Wa+Wb+Wc)=0.11 and Wb / (Wb + Wc) = 0.62.

Synthesis Example 3 [Synthesis of polymer compound (I-2) composed of naphthalene-type tetrafunctional epoxy resin, polyethylene glycol and polyethyleneimine]
As naphthalene type tetrafunctional epoxy resin, EPICLON HP-4700 (Dainippon Ink Chemical Co., Ltd., trade name, epoxy equivalent 158) 7.9 g (50 m equivalent), 4-phenylphenol 5.82 g (31.3 mmol), 65 A 0.21 ml (0.1 mol%) ethyl acetate triphenylphosphonium ethanol solution and 40 ml of N, N-dimethylacetamide were mixed in a flask and reacted at 120 ° C. for 6 hours under a nitrogen atmosphere. After allowing to cool, the solution was dropped into 150 ml of water, and the resulting precipitate was washed twice with methanol and then dried under reduced pressure at 60 ° C. to obtain 15.5 g of a monofunctional epoxy resin.

¹ H-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) is measured, and as a result of considering the integration ratio of epoxy groups, 0.98 oxirane rings remain in one molecule, and it is a monofunctional epoxy resin. It was confirmed.

  To 1.5 g of the obtained monofunctional epoxy resin, 4.5 g of the polymer composed of polyethylene glycol and polyethyleneimine obtained in Synthesis Example 1 above, 15 ml of acetone and 40 ml of methanol are added, and the mixture is heated at 50 ° C. in a nitrogen atmosphere. The reaction was allowed to stir for 2 hours. After completion of the reaction, acetone and methanol were removed under reduced pressure at 40 ° C. to obtain an aqueous solution of a polymer compound (I-2) having a naphthalene type tetrafunctional epoxy resin skeleton.

  The number average molecular weight of the epoxy resin residue (A) of the obtained polymer compound (I-2) is 1070, the average degree of polymerization of the cationic hydrophilic polymer segment is about 233, and the average degree of polymerization of the nonionic hydrophilic segment. Is about 45, the weight of the epoxy resin residue in the polymer compound (I) is Wa, the weight of the cationic hydrophilic polymer segment is Wb, and the weight of the nonionic hydrophilic polymer segment is Wc. /(Wa+Wb+Wc)=0.062 and Wb / (Wb + Wc) = 0.62.

Example 1
100 mg of the polymer compound (I-1) obtained in Synthesis Example 2 was dissolved in 2.0 g of ion-exchanged water, and this solution was cationized by adjusting the pH to 3 with 5N hydrochloric acid. In this solution, C.I. I. A solution prepared by dissolving 50.0 mg of Acid Red 18 (manufactured by Tokyo Chemical Industry Co., Ltd.) in 4.77 g of ion-exchanged water at 70 ° C. was added. Here, the coloring compound C.I. I. The molar ratio of the anionic group in Acid Red 18 to the ethyleneimine unit (cation moiety) in the polymer compound (I-1) was 7.4%. This was stirred at room temperature for 12 hours and then processed using a concentric separator. When the particle size of the obtained particles was measured using FPAR1000 (Otsuka Electronics Co., Ltd.), the average particle size was 163 nm, and the ratio of 90% particle size to 10% particle size was 1.89. This confirmed that the particles were PIC dispersion fine particles having a narrow particle size distribution.

Example 2
In Example 1, instead of the 7.4% molar ratio of the anionic group in Acid Red 18 to the ethyleneimine unit (cation moiety) in the polymer compound (I-1), the ratio was 7.9%. In the same manner as in Example 1, it was confirmed that the PIC dispersion fine particles had a narrow particle size distribution with an average particle size of 180 nm and a ratio of 90% particle size to 10% particle size of 2.39.

Example 3
100 mg of the polymer compound (I-2) obtained in Synthesis Example 3 was dissolved in 2.0 g of ion-exchanged water, and this solution was cationized by adjusting the pH to 1 with 5N hydrochloric acid. In this solution, C.I. I. A solution prepared by dissolving 50.0 mg of Acid Yellow 17 (manufactured by Kanto Chemical Co., Inc.) in 4.77 g of ion-exchanged water at 70 ° C. was added. Here, the coloring compound C.I. I. The molar ratio of the anionic group in Acid Yellow 17 to the ethyleneimine unit (cation moiety) in the polymer compound (I-2) was 8.7%. This was stirred at room temperature for 12 hours and then processed using a concentric separator. When the particle size of the obtained particles was measured using FPAR1000 (Otsuka Electronics Co., Ltd.), the average particle size was 174 nm, and the ratio of 90% particle size to 10% particle size was 2.52. From this, it was confirmed that the particles were PIC dispersion fine particles having a narrow particle size distribution.

Comparative Example 1
100 mg of branched polyethyleneimine (Epomin SP-200, manufactured by Nippon Shokubai Co., Ltd.) was dissolved in 2.0 g of ion-exchanged water, and this solution was cationized by adjusting the pH to 3 with 5N hydrochloric acid. In this solution, C.I. I. A solution prepared by dissolving 50.0 mg of Acid Red 18 in 5.00 g of ion-exchanged water at 70 ° C. was added. Here, the coloring compound C.I. I. The molar ratio of the anionic group in Acid Red 18 to the ethyleneimine unit (cation moiety) was 3.6%. Immediately after mixing, a high-viscosity precipitate was generated from the mixed solution, and the supernatant liquid became almost transparent, so that the coloring compound and the polymer compound were combined by ionic interaction and precipitated. It was judged.

Comparative Example 2
100 mg of the polyethylene glycol-polyethyleneimine copolymer produced in Synthesis Example 1 was dissolved in 2.0 g of ion-exchanged water, and this solution was cationized by adjusting the pH to 3 with 5N hydrochloric acid. In this solution, C.I. I. A solution prepared by dissolving 50.0 mg of Acid Red 18 in 5.00 g of ion-exchanged water at 70 ° C. was added. Here, the coloring compound C.I. I. The molar ratio of the anionic group in Acid Red 18 to the ethyleneimine unit (cation moiety) was 6.0%. When the particle size of the obtained particles was measured using FPAR1000 (Otsuka Electronics Co., Ltd.), the average particle size was 190 nm, and the ratio of 90% particle size to 10% particle size was 8.51. It was found that the particles had a wide particle size distribution.

Comparative Example 3
In Comparative Example 2, the coloring compound used was C.I. I. The same procedure as in Comparative Example 2 was conducted except that Acid Yellow 17 was used and the amount used was 6.5% (molar ratio). When the particle size of the obtained particles was measured using FPAR1000 (Otsuka Electronics Co., Ltd.), the average particle size was 200 nm, and the ratio of 90% particle size to 10% particle size was 7.10. It was found that the particles had a wide particle size distribution.

Test Example In Examples 1 to 3, the fine particle dispersion was taken out and dried under reduced pressure at 80 ° C. and 20 mmHg to obtain a powdered coloring material. When left in this state for about one week, returned to water again and subjected to ultrasonic treatment, a dispersion similar to the dispersion obtained in Examples 1 to 3 was obtained, and the redispersibility and storage stability were improved. It was confirmed that it was excellent.

Claims (11)

A polymer compound (I) having an epoxy resin residue (A), a cationic hydrophilic polymer segment (B) and a nonionic hydrophilic polymer segment (C), and a coloring compound (II) having an anionic group And an aqueous coloring material. The aqueous coloring material according to claim 1, wherein the epoxy resin residue (A) is a residue of a bisphenol A type epoxy resin or a naphthalene type tetrafunctional epoxy resin. The aqueous coloring material according to claim 1, wherein the cationic hydrophilic polymer segment (B) is a segment obtained by cationizing one or more polymers selected from the group consisting of polyethyleneimine, polyvinylamine, polyallylamine and polyvinylpyridine. The aqueous coloring material according to claim 3, wherein the cationic hydrophilic polymer segment (B) is a segment obtained by cationizing polyethyleneimine. Nonionic hydrophilic polymer segment (C) is composed of ethylene glycol, vinyl acetate, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, N-vinylcaprolactam, (meth) acrylamide and (meth) acrylic acid ester. The aqueous coloring material according to claim 1, which is a segment composed of a polymer obtained by polymerizing at least one monomer selected from the group consisting of: The aqueous coloring material according to claim 5, wherein the nonionic hydrophilic polymer segment (C) is a segment made of a polymer obtained by polymerizing ethylene glycol. The number average molecular weight of the epoxy resin residue of the polymer compound (I) is in the range of 300 to 10,000, and the cationic hydrophilic polymer segment (B) and the nonionic hydrophilic polymer segment (C) The polymerization degree of the constituting polymer is independently in the range of 3 to 1,000, and the mass of the epoxy resin residue (A) in the polymer compound (I) is Wa, and the cationic hydrophilic polymer segment ( When the mass of B) is Wb, and the mass of the nonionic hydrophilic polymer segment (C) is Wc, Wa / (Wa + Wb + Wc) = 0.03 to 0.8 and Wb / (Wb + Wc) = 0.1 The aqueous coloring material according to claim 1, which is -0.9. The molar ratio of the anion in the coloring compound (II) having an anionic group to the cation in the cationic hydrophilic polymer segment (B) (anion / cation) is 0.05 to 0.95. The aqueous coloring material according to 1. The aqueous coloring material according to any one of claims 1 to 8, wherein the coloring compound (II) having an anionic group is a compound containing a sulfonic acid alkali metal salt or a carboxylic acid alkali metal salt moiety. The aqueous coloring material according to any one of claims 1 to 9, wherein the epoxy resin residue (A) in the polymer compound (I) is in a colloidal form in which it is hydrophobically associated in an aqueous medium. A powdered coloring material obtained by drying the colloidal aqueous coloring material according to claim 10.